CA1144166A - Basic dioxazine compounds - Google Patents
Basic dioxazine compoundsInfo
- Publication number
- CA1144166A CA1144166A CA000344817A CA344817A CA1144166A CA 1144166 A CA1144166 A CA 1144166A CA 000344817 A CA000344817 A CA 000344817A CA 344817 A CA344817 A CA 344817A CA 1144166 A CA1144166 A CA 1144166A
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- Prior art keywords
- substituted
- alkyl
- unsubstituted
- formula
- group
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
- C09B19/02—Bisoxazines prepared from aminoquinones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/001—Dyes containing an onium group attached to the dye skeleton via a bridge
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Coloring (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Paper (AREA)
Abstract
Abstract Novel dioxazine compounds of the formula (I) in which Z is a basic group, which can be quaternised, Y is an anionic group and X and X1 independently of one another are identical or different substituents from the category comprising: hydrogen, halogen, CN, substituted or unsubstituted alkyl (C1-4); substituted or unsub-stituted phenyl; NHCOR1 in which R1 is alkyl (C1-C4), cycloalkyl, substituted or unsubstituted aryl or a hetero-cyclic radical; and OCOR2 in which R2 is substituted or unsubstituted alkyl (C1-C4) or cycloalkyl; or X and X1 are the group
Description
i~144166 The in~ention relates to novel basic dioxazine compounds, processes for their preparation and their use as dyes for dyeing and printing textile materials, paper and leather and for preparing inks.
According to the invention, there is provided a dioxazine compound of the formula I
X
,~ ~ ~ N~ ~o~ /o~ ~z~ n ~. ~ ~ o / i~ N-J ~ ~ ( ~ m 11 l in which X and Xl independently of each other are identical or different substituents from the category comprising: 1) hydrogen, 2) halogen, 3) cyano, 4) unsubstituted alkyl Cl-C4, 5) unsubstituted phenyl, 6) phenyl substituted li0 by halogen or alkyl Cl-C4, 7) -NHCORl, wherein Rl is alkyl Cl-C4, cycloalkyl, unsubstituted aryl, aryl which is substituted by alkyl Cl-C4, or halogen, or Rl is a heterocyclic radical selected from furan, thiophen, pyridine, quinoline, phenylthiazole or phenyltriazole, 8) OCOR2 in which R2 is unsubstituted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by phenyl or R2 is cycloalkyl, 9) -CONR4.R5 wherein R4 and R5 independently of one another are hydrogen, unsubstituted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by phenyl or NTlT2 or NR15.R16.R17 or R4 and/or R5 is cycloalkyl or aryl or R4 together with R5 and with the inclusion of the N-atom forms a pyrrolidine, piperidine or morpholine ring, 10) -COOR6 wherein R6 is hydrogen, unsubstituted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by OH and phenyl or R6 is cycloalkyl; Y
represents an anionic group selected from the phosphoric acid group, the .~ .
carb~xylic acid group or the sulfonic acid group or a salt form of such a free acid group; benzene nuclei A and Al are optionally substituted by: A) halogen, B) cyano, C~ N02, D~ SCN, E~ unsubstituted alkyl Cl-C8, F) alkyl Cl-C8 substituted by phenyl, G) unsubstituted phenyl, H) phenyl substituted by halogen, COOH, N02, NH2, NHalkyl Cl-C4, N~alkyl Cl-C4)2, alkyl Cl-C4, alkoxy Cl-C4, NHCOphenyl or NHCOalkyl Cl-C4, I) NHCOR18 wherein R18 is unsubstituted alkyl Cl-C4, alkyl Cl-C4 which is substituted by alkoxy Cl-C4, cycloalkyl, OH
or phenyl which phenyl is either unsubstituted or substituted by halogen, alkoxy Cl-C4, alkyl Cl-C4, N02 or CN, or R18 is alkoxy Cl-C4 or cycloalkyl or unsubstituted aryl or aryl which is substituted by chloro or OCH3, K) unsub-stituted benzthiazole or benzthiazole which is substituted by unsubstituted alkyl Cl-C4, unsubstituted alkoxy Cl-C4 or alkoxy Cl-C4 which is substituted by alkoxy Cl-C4, OH or phenyl, L) unsubstituted alkoxy Cl-C4 or alkoxy Cl-C4 which is substituted by OH, alkyl Cl-C4 or alkoxy Cl-C4, M) unsubstituted phenoxy or phenoxy which is substituted by alkyl Cl-C4, N) NHRlg wherein Rlg is hydrogen, unsubstituted aryl or aryl which is condensed with a benzoxazole, benzthiazole or benzimidazole nucleus, or Rlg is benzthiazole, O) S02alkyl Cl-C4, P) CONHR20 wherein R20 is unsubstituted aryl or aryl which is substitu-ted by halogen, phenyl or alkyl Cl-C4; Z is either a basic group of the formula ~Tl -CH2NH-C-alkylene-(Cl-C4) - N
o T2 or I T
-S02-N-alkylene (Cl-C4) - N
or '``''~ ' 1~44~66 1~ Tl -C-N-alkylene (Cl-C4~ - N
or El quaternised group according to the formula -cH2-NH-co-alkylene (Cl C4) or a quaternised group according to the formula IR14 l15 ~ ~3 -S02-N-alkylene (Cl-C4) - N - Rl~ AO
or 114 115 ~3 -co-N-alkylene ~Cl-c4) ~ I R16 AQ
or R15 ~
R17 A~3 in which formulae the symbols have the following meaning: Tl is H or alkyl Cl-C4, which is unsubstituted or substituted by hydroxyl, or Tl is cyclohexyl, unsubstituted or substituted by 1 to 3 methyl radicals, or Tl lS phenyl and T2 is alkyl Cl-C4, which is unsubstituted or substituted by hydroxyl, or the radicals Tl and T2 together with the N atom can also form a pyrrolidine, pyridine, morpholine or piperazine ring, and W is hydrogen, unsubstituted alkyl Cl-C4 or alkyl Cl-C4 substituted by OH or alkoxy Cl-C4, * KO is a radical bf the formula -2a-., -- --~ .
, R7 Rg Rll - N I 1 12 e R8 Rlo R13 R7 and R8 independently of one another are unsubstituted alkyl Cl-C4, alkyl Cl-C4 substituted by OH, CONH2 or CN or unsubstituted cycloalkyl, Rg and Rlo independently of each other are hydrogen, unsubstituted alkyl Cl-C4, cycloalkyl or acyl, Rll is hydrogen, unsubstituted alkyl Cl-C4, alkyl Cl-C~ substituted by OH, unsubstituted cycloalkyl or unsubstituted aryl, and R12 is hydrogen, unsubstituted alkyl Cl-C4, alkyl Cl-C4 substituted by OH, unsubstituted cycloalkyl, unsubstituted alkoxy Cl-C4 or unsubstituted aryl, Rl3 is unsubstitu-ted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by OH, CONH2, NH2 or Rl3 ~is alkoxy Cl-C4, or R7 and R8 or R7 and Rg or R8 and Rlo or Rll and R12 to-gether with the N atom, form a piperidine, pyrrolidine or morpholine ring or Rll, R12 and R13 with the inclusion of the N atom form a heterocyclic ring of the formula~
N
.
~3 N / i ~3 ~ - S - N - N
unsubsti.tuted pyridine or pyridine which is substitu~ed by CH3) OH, NH2, COOH
or CN, R14 is hydrogen or unsubstituted alkyl Cl-C4, R15 and R17 are each unsubstituted alkyl C]-C4 or cycloalkyl and R16 is unsubstituted alkyl Cl-C4, cycloalkyl, alkoxy Cl-C4 or NH2, or two of the radicals R15, R16 and/or R17, together with the nitrogen atom, form an unsubstituted pyridine ring or -2b-.
~144~66 pyridine which i5 substituted by CH3, OH, NH2, COOH or CN; n is a number from 1 to 4 and m is a number fro~ 0 to 2, with the proviso that the number m is small than n.
An alkyl group X or Xl is an unbranched or branched alkyl group having 1 to 4 carbon atoms, which can be substituted; it is, for example, the methyl, ethyl, n-propyl, iso-propyl or n-, sec.- or tert.-butyl group;
a substituted or unsubstituted phenyl group X or Xl is unsubstituted -2c-,,~.~ .,~ .
.
.
phenyl or a phenyl group which is substituted, ~or example, by alkyl groups, which are branched or unbranched and have 1 to 4 carbon atoms, or halogen, such as fluorine, chlorine or bromine; a NHCORl group X or Xl in which Rl is alkyl (Cl-C4), cycloalkyl, substituted or unsubsti-tuted aryl or a heterocyclic ring is, for example, the methyl-, ethyl-, cyclohexyl-, phenyl-, alkylphenyl- or halogenophenyl-carbonylamino radical or the furan-, thiophene-, pyridine-, quinoline-, phenylthiazole- or phenyltriazole-carbonylamino radical and in particular the o-chlorophenyl- or methyl-carbonylamino radical.
A OCOR2 group X or Xl is, for example, one of the following radicals: OCO.CH~; OCO.C2H5; OCO.C3 ~ (n and iso) and OCO.C4Hg (n and iso) and also OCO.CH2.C6H5 and OCO.cyclohexyl; a /R4 group X or Xl is, for -CO-N\
example: CONH2 or CONHC6H5; and a COOR6 group X or Xl is, for example, one of the following radicals: COOH, COOCH3 and COOC2H5, in which the alkyl radicals can also be sub-stituted by, for example, OH or C6H5.
In preferred dioxazine compounds, X and Xl are identica~ substituents; in particular X and Xl are H, Cl, Br, CONH2, CONHC6H5, NHCOC6H4Cl, NH.CO-thiophene, CN, COO-alkyl, in particular COOCH3 and COOC2H5, NHCOCH3, OCOCH3 or alkyl, in particular CH3 and C2H5, or COOH;
compounds of particular interest are those in which X and Xl are each a NHCORl group in which Rl is alkyl (Cl-C4) or substituted or unsubstituted aryl, or X and Xl are each, in particular, halogen, especially chlorine.
The benzo radicals A and/or Al can be identical or different and can have one or more further substituents, in addition to the groups Z and Y. Examples of possible substituents are: halogen, such as fluorine, chlorine or bromine; CN; and alkyl having 1 to 8 carbon atoms which can be unsubstituted or substituted, for example by phenyl;
further possible substituents in A/Al are: unsubstituted phenyl and phenyl which can be substituted by, for example, halogen,such as fluorine, chlorine or bromine; or by COOH, N02, NH2 or NH2 which is monosubstituted or disubsti-tuted on the N atom, for example substituted by alkyl (Cl-C4); and also NHCO-alkyl (Cl-C4) or NHCO-C6H5;
furthermore, the phenyl in A/Al can be substituted by alkoxy (Cl-C4) or alkyl (Cl-C4); or A/Al can be substi-tuted by NHCOR18 in which R18 is unsubstituted alkyl or alkyl which is substituted by, for example, phenyl, alkoxy, cycloalkyl, unsubstituted aryl or substituted aryl, for example unsubstituted phenyl or phenyl which is substituted by halogen, alkoxy, alkyl, NO2 or CN; further substituents in A and/or Al are: NO2, SCN, heterocyclic rings, for example the benzthiazole radical, which can also be further substituted, for example by alkyl (Cl-C4); and also aIkoxy groups, such as the methoxy, ethoxy or n- or iso-propoxy group, which alkoxy groups can also be substituted by, for example, further alkoxy groups or by OH or phenyl;
further possible groups are the phenoxy group, which is unsubstituted or substituted (for example by alkyl), and the group NHRlg~ in which Rlg is hydrogen or aryl, in par-ticular phenyl, which can be substituted or fused with hetero-rings, for example to form a benzoxazole, benzthia-zole or benzimidazole, or Rlg is a hetero-ring, for example the benzthiazole ring. Finally, A and/or Al can also be further substituted by an alkylsulfonyl group or by the group CONHR20, in which R20 is a substituted or unsubsti-tuted aryl radical, such as the unsubstituted phenyl radi-cal or a phenyl radical which is substituted by halogen, such as fluorine, chlorine or bromine, or by phenyl, methyl or ethyl.
In preferred dioxazine compounds the two benzo radicals A and Al are substituted by one or more identical substituents, in particular by Cl, NHCOC6H5, NHCOC6H4Cl, NHCOC6H4.0CH3, alkoxy (Cl-C3) or alkoxy (Cl-C3) substituted by OH or alkoxy or by alkyl, in particular CH3; -O.C6H5, 6 4 3' 6 5' 2 C6 5 nd HC yl~ P
lar -NHCO.C3H7.
As a basic group which can be quaternised, Z is, for example:
a) as a basic group, the radicals -CH2NH-R-alkYlene-(Cl-c4) ~\T
or W
-SO2-N-alkylene (Cl-C4) - N~
or W T
-C-N-alkylene (Cl-C4) N~T
in which Tl is H or a low-molecular alkyl radical, which is unsubstituted or substituted by hydroxyl, or a cyclo-hexyl radical, which is unsubstituted or substituted by 1 to 3 methyl radicals, or a phenyl radical; and T2 is a low-molecular alkyl radical which is unsubstituted or substituted by hydroxyl; or the radicals Tl and T2 together with the N atom can also form a pyrrolidine, pyridine, morpholine or piperazine ring; and W is hydro-gen, an unsubstituted alkyl group having 1 to 4 carbon atoms or an alkyl group (Cl-C4) substituted by, for example, OH or alkoxy (C1-C~); the radical T
- N\ 1 being, ~or example, one of the ~ollowing radicals:
-N -~CH3)2 -N ~ (C2H5)2 114~i66 - ~\ H /O
-N`:HI
- ~ H \-\
-N-(C2H40H)2 b) as a quaternised group, for example, the radical of the formula:
-CH2-NH-CO-alkylene(Cl-C4)-K ~ A
in which K ~ is a radical of the formula ~ Rg ~ ~11 - N N or - N - R12 . 8 10 13 in which R7 and R8 independently of one another are a substituted or unsubstituted alkyl group (C1-C4) or a substituted or unsubstituted cycloalkyl group, or R7 together with R8 and with the inclusion of the N atom forms a heterocyclic ring; Rg and Rlo independently of one another are hydrogen, substituted or unsubstituted alkyl (Cl-C4) or cycloalkyl or an acyl group; Rll is hydrogen, substituted or unsubstituted alkyl (Cl-C4), substituted or unsubstituted cycloalkyl or substituted or unsubstituted aryl; and R12 is hydrogen, substituted or unsubstituted alkyl (Cl-C4), substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryl; or R7 and Rg and/or R8 and Rlo, together with the N atom, form a heterocyclic ring, or ~, 11 12 Rll, R12 and Rl3, with the inclusion of the N atom, form a heterocyclic ring; the radical K ~ being, for example, a radical of the formula:
-N (CH3) 3 -N~ N (CH3) 2 (~)(C2H5) 3 -~ H \- -(~(C2H5) 2 3( ~ (3/-~ j -(~)(C2H40H) 2 -(~?~H3 ) 2 -~ H \O
2H~5 H3 H2_ .
N~
HC CE~
According to the invention, there is provided a dioxazine compound of the formula I
X
,~ ~ ~ N~ ~o~ /o~ ~z~ n ~. ~ ~ o / i~ N-J ~ ~ ( ~ m 11 l in which X and Xl independently of each other are identical or different substituents from the category comprising: 1) hydrogen, 2) halogen, 3) cyano, 4) unsubstituted alkyl Cl-C4, 5) unsubstituted phenyl, 6) phenyl substituted li0 by halogen or alkyl Cl-C4, 7) -NHCORl, wherein Rl is alkyl Cl-C4, cycloalkyl, unsubstituted aryl, aryl which is substituted by alkyl Cl-C4, or halogen, or Rl is a heterocyclic radical selected from furan, thiophen, pyridine, quinoline, phenylthiazole or phenyltriazole, 8) OCOR2 in which R2 is unsubstituted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by phenyl or R2 is cycloalkyl, 9) -CONR4.R5 wherein R4 and R5 independently of one another are hydrogen, unsubstituted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by phenyl or NTlT2 or NR15.R16.R17 or R4 and/or R5 is cycloalkyl or aryl or R4 together with R5 and with the inclusion of the N-atom forms a pyrrolidine, piperidine or morpholine ring, 10) -COOR6 wherein R6 is hydrogen, unsubstituted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by OH and phenyl or R6 is cycloalkyl; Y
represents an anionic group selected from the phosphoric acid group, the .~ .
carb~xylic acid group or the sulfonic acid group or a salt form of such a free acid group; benzene nuclei A and Al are optionally substituted by: A) halogen, B) cyano, C~ N02, D~ SCN, E~ unsubstituted alkyl Cl-C8, F) alkyl Cl-C8 substituted by phenyl, G) unsubstituted phenyl, H) phenyl substituted by halogen, COOH, N02, NH2, NHalkyl Cl-C4, N~alkyl Cl-C4)2, alkyl Cl-C4, alkoxy Cl-C4, NHCOphenyl or NHCOalkyl Cl-C4, I) NHCOR18 wherein R18 is unsubstituted alkyl Cl-C4, alkyl Cl-C4 which is substituted by alkoxy Cl-C4, cycloalkyl, OH
or phenyl which phenyl is either unsubstituted or substituted by halogen, alkoxy Cl-C4, alkyl Cl-C4, N02 or CN, or R18 is alkoxy Cl-C4 or cycloalkyl or unsubstituted aryl or aryl which is substituted by chloro or OCH3, K) unsub-stituted benzthiazole or benzthiazole which is substituted by unsubstituted alkyl Cl-C4, unsubstituted alkoxy Cl-C4 or alkoxy Cl-C4 which is substituted by alkoxy Cl-C4, OH or phenyl, L) unsubstituted alkoxy Cl-C4 or alkoxy Cl-C4 which is substituted by OH, alkyl Cl-C4 or alkoxy Cl-C4, M) unsubstituted phenoxy or phenoxy which is substituted by alkyl Cl-C4, N) NHRlg wherein Rlg is hydrogen, unsubstituted aryl or aryl which is condensed with a benzoxazole, benzthiazole or benzimidazole nucleus, or Rlg is benzthiazole, O) S02alkyl Cl-C4, P) CONHR20 wherein R20 is unsubstituted aryl or aryl which is substitu-ted by halogen, phenyl or alkyl Cl-C4; Z is either a basic group of the formula ~Tl -CH2NH-C-alkylene-(Cl-C4) - N
o T2 or I T
-S02-N-alkylene (Cl-C4) - N
or '``''~ ' 1~44~66 1~ Tl -C-N-alkylene (Cl-C4~ - N
or El quaternised group according to the formula -cH2-NH-co-alkylene (Cl C4) or a quaternised group according to the formula IR14 l15 ~ ~3 -S02-N-alkylene (Cl-C4) - N - Rl~ AO
or 114 115 ~3 -co-N-alkylene ~Cl-c4) ~ I R16 AQ
or R15 ~
R17 A~3 in which formulae the symbols have the following meaning: Tl is H or alkyl Cl-C4, which is unsubstituted or substituted by hydroxyl, or Tl is cyclohexyl, unsubstituted or substituted by 1 to 3 methyl radicals, or Tl lS phenyl and T2 is alkyl Cl-C4, which is unsubstituted or substituted by hydroxyl, or the radicals Tl and T2 together with the N atom can also form a pyrrolidine, pyridine, morpholine or piperazine ring, and W is hydrogen, unsubstituted alkyl Cl-C4 or alkyl Cl-C4 substituted by OH or alkoxy Cl-C4, * KO is a radical bf the formula -2a-., -- --~ .
, R7 Rg Rll - N I 1 12 e R8 Rlo R13 R7 and R8 independently of one another are unsubstituted alkyl Cl-C4, alkyl Cl-C4 substituted by OH, CONH2 or CN or unsubstituted cycloalkyl, Rg and Rlo independently of each other are hydrogen, unsubstituted alkyl Cl-C4, cycloalkyl or acyl, Rll is hydrogen, unsubstituted alkyl Cl-C4, alkyl Cl-C~ substituted by OH, unsubstituted cycloalkyl or unsubstituted aryl, and R12 is hydrogen, unsubstituted alkyl Cl-C4, alkyl Cl-C4 substituted by OH, unsubstituted cycloalkyl, unsubstituted alkoxy Cl-C4 or unsubstituted aryl, Rl3 is unsubstitu-ted alkyl Cl-C4 or alkyl Cl-C4 which is substituted by OH, CONH2, NH2 or Rl3 ~is alkoxy Cl-C4, or R7 and R8 or R7 and Rg or R8 and Rlo or Rll and R12 to-gether with the N atom, form a piperidine, pyrrolidine or morpholine ring or Rll, R12 and R13 with the inclusion of the N atom form a heterocyclic ring of the formula~
N
.
~3 N / i ~3 ~ - S - N - N
unsubsti.tuted pyridine or pyridine which is substitu~ed by CH3) OH, NH2, COOH
or CN, R14 is hydrogen or unsubstituted alkyl Cl-C4, R15 and R17 are each unsubstituted alkyl C]-C4 or cycloalkyl and R16 is unsubstituted alkyl Cl-C4, cycloalkyl, alkoxy Cl-C4 or NH2, or two of the radicals R15, R16 and/or R17, together with the nitrogen atom, form an unsubstituted pyridine ring or -2b-.
~144~66 pyridine which i5 substituted by CH3, OH, NH2, COOH or CN; n is a number from 1 to 4 and m is a number fro~ 0 to 2, with the proviso that the number m is small than n.
An alkyl group X or Xl is an unbranched or branched alkyl group having 1 to 4 carbon atoms, which can be substituted; it is, for example, the methyl, ethyl, n-propyl, iso-propyl or n-, sec.- or tert.-butyl group;
a substituted or unsubstituted phenyl group X or Xl is unsubstituted -2c-,,~.~ .,~ .
.
.
phenyl or a phenyl group which is substituted, ~or example, by alkyl groups, which are branched or unbranched and have 1 to 4 carbon atoms, or halogen, such as fluorine, chlorine or bromine; a NHCORl group X or Xl in which Rl is alkyl (Cl-C4), cycloalkyl, substituted or unsubsti-tuted aryl or a heterocyclic ring is, for example, the methyl-, ethyl-, cyclohexyl-, phenyl-, alkylphenyl- or halogenophenyl-carbonylamino radical or the furan-, thiophene-, pyridine-, quinoline-, phenylthiazole- or phenyltriazole-carbonylamino radical and in particular the o-chlorophenyl- or methyl-carbonylamino radical.
A OCOR2 group X or Xl is, for example, one of the following radicals: OCO.CH~; OCO.C2H5; OCO.C3 ~ (n and iso) and OCO.C4Hg (n and iso) and also OCO.CH2.C6H5 and OCO.cyclohexyl; a /R4 group X or Xl is, for -CO-N\
example: CONH2 or CONHC6H5; and a COOR6 group X or Xl is, for example, one of the following radicals: COOH, COOCH3 and COOC2H5, in which the alkyl radicals can also be sub-stituted by, for example, OH or C6H5.
In preferred dioxazine compounds, X and Xl are identica~ substituents; in particular X and Xl are H, Cl, Br, CONH2, CONHC6H5, NHCOC6H4Cl, NH.CO-thiophene, CN, COO-alkyl, in particular COOCH3 and COOC2H5, NHCOCH3, OCOCH3 or alkyl, in particular CH3 and C2H5, or COOH;
compounds of particular interest are those in which X and Xl are each a NHCORl group in which Rl is alkyl (Cl-C4) or substituted or unsubstituted aryl, or X and Xl are each, in particular, halogen, especially chlorine.
The benzo radicals A and/or Al can be identical or different and can have one or more further substituents, in addition to the groups Z and Y. Examples of possible substituents are: halogen, such as fluorine, chlorine or bromine; CN; and alkyl having 1 to 8 carbon atoms which can be unsubstituted or substituted, for example by phenyl;
further possible substituents in A/Al are: unsubstituted phenyl and phenyl which can be substituted by, for example, halogen,such as fluorine, chlorine or bromine; or by COOH, N02, NH2 or NH2 which is monosubstituted or disubsti-tuted on the N atom, for example substituted by alkyl (Cl-C4); and also NHCO-alkyl (Cl-C4) or NHCO-C6H5;
furthermore, the phenyl in A/Al can be substituted by alkoxy (Cl-C4) or alkyl (Cl-C4); or A/Al can be substi-tuted by NHCOR18 in which R18 is unsubstituted alkyl or alkyl which is substituted by, for example, phenyl, alkoxy, cycloalkyl, unsubstituted aryl or substituted aryl, for example unsubstituted phenyl or phenyl which is substituted by halogen, alkoxy, alkyl, NO2 or CN; further substituents in A and/or Al are: NO2, SCN, heterocyclic rings, for example the benzthiazole radical, which can also be further substituted, for example by alkyl (Cl-C4); and also aIkoxy groups, such as the methoxy, ethoxy or n- or iso-propoxy group, which alkoxy groups can also be substituted by, for example, further alkoxy groups or by OH or phenyl;
further possible groups are the phenoxy group, which is unsubstituted or substituted (for example by alkyl), and the group NHRlg~ in which Rlg is hydrogen or aryl, in par-ticular phenyl, which can be substituted or fused with hetero-rings, for example to form a benzoxazole, benzthia-zole or benzimidazole, or Rlg is a hetero-ring, for example the benzthiazole ring. Finally, A and/or Al can also be further substituted by an alkylsulfonyl group or by the group CONHR20, in which R20 is a substituted or unsubsti-tuted aryl radical, such as the unsubstituted phenyl radi-cal or a phenyl radical which is substituted by halogen, such as fluorine, chlorine or bromine, or by phenyl, methyl or ethyl.
In preferred dioxazine compounds the two benzo radicals A and Al are substituted by one or more identical substituents, in particular by Cl, NHCOC6H5, NHCOC6H4Cl, NHCOC6H4.0CH3, alkoxy (Cl-C3) or alkoxy (Cl-C3) substituted by OH or alkoxy or by alkyl, in particular CH3; -O.C6H5, 6 4 3' 6 5' 2 C6 5 nd HC yl~ P
lar -NHCO.C3H7.
As a basic group which can be quaternised, Z is, for example:
a) as a basic group, the radicals -CH2NH-R-alkYlene-(Cl-c4) ~\T
or W
-SO2-N-alkylene (Cl-C4) - N~
or W T
-C-N-alkylene (Cl-C4) N~T
in which Tl is H or a low-molecular alkyl radical, which is unsubstituted or substituted by hydroxyl, or a cyclo-hexyl radical, which is unsubstituted or substituted by 1 to 3 methyl radicals, or a phenyl radical; and T2 is a low-molecular alkyl radical which is unsubstituted or substituted by hydroxyl; or the radicals Tl and T2 together with the N atom can also form a pyrrolidine, pyridine, morpholine or piperazine ring; and W is hydro-gen, an unsubstituted alkyl group having 1 to 4 carbon atoms or an alkyl group (Cl-C4) substituted by, for example, OH or alkoxy (C1-C~); the radical T
- N\ 1 being, ~or example, one of the ~ollowing radicals:
-N -~CH3)2 -N ~ (C2H5)2 114~i66 - ~\ H /O
-N`:HI
- ~ H \-\
-N-(C2H40H)2 b) as a quaternised group, for example, the radical of the formula:
-CH2-NH-CO-alkylene(Cl-C4)-K ~ A
in which K ~ is a radical of the formula ~ Rg ~ ~11 - N N or - N - R12 . 8 10 13 in which R7 and R8 independently of one another are a substituted or unsubstituted alkyl group (C1-C4) or a substituted or unsubstituted cycloalkyl group, or R7 together with R8 and with the inclusion of the N atom forms a heterocyclic ring; Rg and Rlo independently of one another are hydrogen, substituted or unsubstituted alkyl (Cl-C4) or cycloalkyl or an acyl group; Rll is hydrogen, substituted or unsubstituted alkyl (Cl-C4), substituted or unsubstituted cycloalkyl or substituted or unsubstituted aryl; and R12 is hydrogen, substituted or unsubstituted alkyl (Cl-C4), substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy or substituted or unsubstituted aryl; or R7 and Rg and/or R8 and Rlo, together with the N atom, form a heterocyclic ring, or ~, 11 12 Rll, R12 and Rl3, with the inclusion of the N atom, form a heterocyclic ring; the radical K ~ being, for example, a radical of the formula:
-N (CH3) 3 -N~ N (CH3) 2 (~)(C2H5) 3 -~ H \- -(~(C2H5) 2 3( ~ (3/-~ j -(~)(C2H40H) 2 -(~?~H3 ) 2 -~ H \O
2H~5 H3 H2_ .
N~
HC CE~
2 2 -NiC2H40H)3 ~ H ~
~ H ~H2-' ~3 ~3--- (3-----~1 (C2H40H) 2 -~ H ~0 -1~ H ~-~ ' - ~H 2- -(~CH3 ~3 . .
-~--CH20H ~ 1 2 4CONEI2) 2 2HS 2H4CONH2 ~2 -g~CH3) 2 \ ~ ( 2 4CN) 2 2}I4-CONH (C~3~OH~N~2ICOOE~C~t) 2 -(~)(C~3 ) 2 -GN~
2H40EI ./ \. \ /
--(C~3 ? 2 -~ (CH3 3 2
~ H ~H2-' ~3 ~3--- (3-----~1 (C2H40H) 2 -~ H ~0 -1~ H ~-~ ' - ~H 2- -(~CH3 ~3 . .
-~--CH20H ~ 1 2 4CONEI2) 2 2HS 2H4CONH2 ~2 -g~CH3) 2 \ ~ ( 2 4CN) 2 2}I4-CONH (C~3~OH~N~2ICOOE~C~t) 2 -(~)(C~3 ) 2 -GN~
2H40EI ./ \. \ /
--(C~3 ? 2 -~ (CH3 3 2
3 2 4 H2 or Z is a cationic group of the ~ormula R R
l14 l15 1 ~
-S02-N-alXylene tCl-C4)- N - R161 A t3 in which "alkylene" is an alkylene bridge which can be interrupted by -O-, -S-, -NH- or -N- ; R14 is ; alkyl(Cl-C4) hydrogen or a substituted or unsubstituted alkyl radical;
R15 and R17 are each a substituted or unsubstituted alkyl radical (Cl-C4) or a cycloalkyl radical and R16 is a substituted or unsubstituted alkyl radical (Cl-C4), a cycloalkyl radical, an alkoxy radical or a NH2 group;
or two of the radicals R15, R16 and/or R17, together with the nitrogen atom, form a heterocyclic ring; or Z is a cationic group of the formula ,., g -CO-~ - al~ylene(Cl-C4) - ~ - R16]
R17 A~
or llS ~ A
R
_ 17 in which the symbols R14, alkylene, R15, R16 and R17 a as defined above, and in which A ~ is an anion in every case If Z is a quaternised basic group, anions A are either inorganic or organic anions; examples are:
halide ions, such as chloride, bromide or iodide ions, and sulfate, methylsulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, molybdophosphate, tungstophosphate, tungstomolybdophosphate, benzene-sulfonate, naphthalenesulfonate, 4-chlorobenzene-sulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as that of zinc chloride double salts.
Preferred anions are, depending on the way in which the compounds are used, for example the acetate ion and chloride ion (for textile and paper materials) and the chloride ion for the preparation of inks In preferred dioxazine compounds, Z is a quater-nised basic group or a radical containing such a group and n is the number 2 or 3.
An anionic group Y is, for example, the phosphoric acid group, the carboxylic acid group or the sulfonic acid group or a salt form, such as the Na, K, Li or NH4 salt, of this free acid group In preferred dioxazine compounds, m is the number O and Y is the SO3H group or a salt form thereof.
Dioxazine compounds of particular interest have the formula I in which Z is a cationic group, n is the number 2 or ~, m is the number O and X and Xl are each Cl, and in which A and Al have the same substituents.
The basic dioxazine compounds of the formula I, which can be quaternised, are compounds which are charac-terised by brilliant red to blue shades, by the fact that they are not sensitive to the degree of hardness of water and by a high affinity for, in particular, cellulose materials; furthermore, the addition of fixing agents to the application bath is not necessary for the application of these dioxazine compounds.
The basic dioxazine compounds of the formula I, which can be quaternised, are prepared in a known manner One possibility comprises, for example, a) introducing a basic group Z, which can be quate~nised, into a compound of the formula II
X
~-~ /N~ /o~
in which the symbols A, Al, X and Xl are as defined under formula I, then, if Y is not yet-present, introducing an anionic group Y if necessary and, if necessary, quaternis-ing the quaternisable basic group Z with a quaternising agent, or b~ subjecting a compound of the formula III
X' C~ o (III) O~ C1 X;
in which X~ and Xl are the same as X and Xl but are not 114~166 CN, to a condensation reaction with at least a mols of a compound A-NH2 and b mols of a compound Al-NH2, the sum of a and b being at least 2 and the said compounds A-NH2 and Al-NH2 containing n basic groups Z, which can be quaternisable, or n already quaternised basic groups Z, the reaction proceeding with cyclisation to form a dioxazine compound, quaternising a quaternisable basic group Z, which may be present, with a quaternising agent and, if necessary, introducing an anionic group Y, With regard to process variant a), the starting compounds of the formula II are known both with and with-out an anionic group Y (for example U.S. Patent Specifica-tions 2,016,504, 2,082,344 and 2,026,092) and can be obtained in a known manner. The introduction of a quaternisable basic group Z or the introduction of a group Z which contains a quaternisable group is likewise effec-ted in a known manner, for example by reacting the com-pound of the formula II with N-methylolchloroacetamide in concentrated X2S04 or phosphoric acid, if necessary in the pre~ence of P205, at 0-50C and preferably at room tem-perature, or by first introducing the S02Cl group into the compound of the formula II in a conventional manner (for example using chlorosulfonic acid at 100-150C) and then aminating, or by introducing the -CH2Cl group into the compound of the formula II and then aminating Basic groups suitable as a quaternisable basic group Z are all basic groups which are capable of taking up protons during the dyeing process so that they are con-verted to cationic groups. Examples of such compounds which introduce a basic quaternisable group Z are N-methylolchl~acetamide with subsequent reaction with an amine such as pyridine; alternatively the radical -S02Cl is first introduced into the molecule, for example using chlorosulfonic acid, and the compound is then reacted with a diamine, for example 3-dimethylamino-1-propylamine.
If it is desired to convert the quaternisable basic group ~ in the compound of the formula II into a 1149~166 quaternised group, the quaternisation is likewise e~fected in a known manner, for example using quaternising agents in an inert solvent, such as chlorobenzene, or, if desired, in aqueous suspension, or without a solvent in an excess of the quaternising agent, at a temperature of about 20 to 120C.
Suitable quaternising agents are, for example, alkyl halides, such as methyl chloride or ethyl chloride, methyl bromide, ethyl bromide or butyl bromide or methyl iodide or ethyl iodide, and in particular alkyl sulfates, such as dimethyl sulfate, diethyl sulfate and dibutyl sulfate, or benzyl chloride, chloracetamide, acrylates, epoxides, such as ethylene oxide, epichlorohydrin, alkyl esters of aromatic sulfonic acids, such as methyl p-toluenesulfonate or methyl benzenesulfonate, and also the propyl and butyl esters of benzenesulfonic acid If the compounds of the formula II do not contain an anionic group Y,these groups Y can advantageously be introduced prior to the quaternisation reaction for the conversion of the quaternisable group to a quaternised group Z. This is effected, for example, by sulfonation with sulfuric acid or, in order to introduce a phosphoric acid group, by the procedure of U.S. Patent Specification 2,845,420 After the quaternisation and the introduction of the anionic group Y, which may be carried out, the dioxazine compounds of the formula I are separated from the reaction medium and dried.
With regard to procedure b), the starting material used in this case is the compound of the formula III, which is sub~ected to a condensation reaction with a mols of A-NH2 and b mols of Al-NH2, with cyclisation, in a known manner (K,Venkataraman, Volume II (1952) page 786 "The Chemistry of Synthetic Dyes" NY ). If X and/or X
in the end product of the formula I are CN, such compounds are prepared, for example, by subjecting the compound of the formula IIIa ,., li49~66 O~ \ ~ \Cl (IIIa) to a condensation reaction with a mols of A-NH2 and b mols of Al-NH2, with cyclisation, in accordance with the above instructions, and then replacing the two Cl atoms by CN
groups, for example by reacting the condensation product with CuCN in a known manner, for example in accordance with the procedure of German Offenlegungsschrift 2,733,539 If the amines A-NH2 and Al-MH2 contain a quater-nisable basic group Z, the latter can be converted to a quaternised group by a procedure analogous to those des-cribed above; if necessary, an anionic group Y is then also introduced, as described further above Because of these process measures it is possible to prepare dioxazine compounds of the formula I in which the two symbols A have identical or different substitu-ents. In addition, it is also possible to prepare mix- -tures which contain dioxazine compounds of the formula I
in which the two symbols A have the same substituents and dioxazine compoundS of the formula I in which the two symbols A have different substituents.
The novel, basic dioxazine compounds of the for-mula I, which can be quaternised, are used as dyes for dyeing and printing textile materials, paper and leather and for preparing inks, If these dyes are used for dyeir~g and printing textile materials, the materials which can be dyed are wool, silk and acid-modified polyamide materials, and also polyacrylonitrile materials, in particular wet cable, and modified polyester material which can be dyed with basic dyes. However, the materials are in particular natural and regenerated cellulose materials, especially cotton and viscose, on which red to blue dyeings, which are brilliant in some cases, are obtained, Tne dioxazine 1144~66 compounds of the formula I according to the invention have a good uptake, good exhaustion and good build-up on these textile materials, and in particular on the said cellu-lose materials, and the resulting dyeings have very good fastness properties, in particular wet fastness properties, such as fastness to washing, and fastness to light.
With the basic dioxazine dyes, the wet fastness properties can be even further improved if necessary, by rendering the dyes insoluble, for example by means of an alkaline after-treatment on the fibre. Furthermore, it is an advantage that the dioxazine compounds of the formula I
according to the invention are taken up by the cellulose materials without pre-treatment of the said materials and without additional addition of salt to the dye liquor, The dioxazine compounds of the formula I according to the invention are also used for dyeing paper of all types, in particular bleached, unsized and sized, lignin-free paper These compounds are very particularly suit-able for dyeing unsized paper (tissues) because of their very high standard affinity for this substrate.
The dioxazine compounds according to the invention are taken up very well by these substrates and the waste water remains colourless - even in the case o~ deep shades (to more than 1/1 SD = standard depth of dyeing) -and this is an eminent technical and ecological advantage, especially with regard to the current laws relating to effluents. The good uptake is also advantageous for good reproducibility of the shade, The hardness of the water has virtually no influence on the uptake. The dyeings are fast to wet processing, i,e. they show no tendency to staining when dyed paper in the wet state is brought into contact with moist white paper. This characteristic is particularly desirable for so-called tissues, with which it is foreseeable that the dyed paper will come into contact in the wet state (for example saturated with water, alcohol, surfactant solution or the like) with other sur~aces such as textiles, paper and the ,, ~144166 like, which have to be protected against soiling The high affinity for paper and the high rate of exhaustion of the dioxazine dyes according to the inven-tion are a great advantage for the continuous dyeing of paper and thus make possible a wider application of this known, highly economical process, which has the following advantages:
a) simpler and more rapid correction of the shade and thus less loss of paper which does not conform to type (wast-age) compared with the discontinuous dyeing of paper pulp;
b) better constancy of the shade; (no "tailing") and c) if the dye is metered in just upstream of the flow box, in the low-density pulp, thorough cleaning of the beater, the blending chest and the like after each batch can be dispensed with, thus shortening the process and stream-lining the procedure at the same time.
The dioxazine compounds of the formula I are also used for dyeing leather materials by very diverse applica-tlon processes? such as spraying, brushing and immersion, and for the preparation of inks of all types, such as for ballpoint pens and printing inks Finally, the novel dioxazine compounds of the formula I are also suitable for bulk dyeing linear syn-thetic high-molecular weight polyamides, such as poly-hexamethyleneadipamide, Dyeing of the polyamide chips is effected, in particular, from an aqueous bath in the presence of wetting agents or dispersing agents and, if desired, salts, with subsequent melting and shaping.
With regard to the reducible characteristics o~
the molten high-molecular weight polyamide melts and the high melt temperature (about 270-300C), the use of these dyes of the formula I constitutes a surprising enrichment of the art.
The following examples illustrate the invention without restricting it thereto, The temperatures are in degrees centigrade and parts (P) and percentages are by weight.
~1~4166 -- 16 _ Example 1: A mixture of 57 P of the compound of the formula Cl ._.
/o~ /o-.~ ~-.~.. ;o~ C~3 Cl (the condensation product of chloranil and l-amino-2,4-o-methylphenoxy-benzene) and 28 P of N-methylolchloro-acetamide is introduced at 0-5 into 500 P of 90% sulfuric acid and the mixture is stirred at 0-5 for 15 hours.
The reaction product is precipitated on ice and is filtered off again, with suction, and washed with water After drying, this yields 72 P of the compound of the formula:
Cl I t~-`t~N~t~!~-/`-' ~t' '~ --~ca2~CC~2cl)2 ~ - 3 --~C~Cl 60 P of the product thus obtained are introduced into 400 P of pyridine and the mixture is warmed at 100 for 1 hour. The dye of the formula:
o\ ~ o_.~ ~ ~. ~ 2N~C~C~2~ ~ ~3 2 1 11 i i i1 ~ - ~/-~t~ - C~3 2Cl~
L ~ C~3 Cl which has precipitated is filtered off with suction and dried. It displays a very good uptake on paper and cotton, and the pale red dyeings have a good spectrum of fastness properties, .
.
~ . ~
li44:16~i When the above example is repeated replacing pyridine by a- or Y-picoline or by a mixture of a-/Y-picoline or by triethylenediamine or N,N-dimethylhydrazine or N,N-dimethylethanolamine, similar dyes are obtained which have equally good coloristic properties When the 57 P of the condensation product of chloranil and l-amino-2,4-o-methylphenoxy-benzene are replaced by equivalent parts of the condensation products listed in Table 1 below and these products are reacted with 28 P of N-methylolchloroacetamide and the reaction products are aminated with pyridine, an otherwise iden-tical procedure yields cationic dioxazine dyes of the formula indicated in column 3; the colour shade of these dyes on cotton is indicated in the last column of the table.
~44~66 ~ o o a) a~
o ~ h S-~ 3 :
:~: s s s ~ , . C,=.~ ~
' .
. .
I ~f ~_ _ il44166 og o c~ h ~ h _. _, U~ ~
_ --/ O ~ ~ : :' 5 ¢.~
.4 U~ O
I __ ~
. ~ . -- _ I ~5 ~ ~--~ a ~ a .~ __ _ . ..
1~ ~D r t~ ~ O
.. .
~144166 O g ~1 ~0 ~ ~ ~ ~ O
o h ~ h h 5 ~ o ~ s ~ , .
¦ ~ ~ ~ C' ~
~ ~._.~" . _ _ I ~ 0 r X -- ~ ~ ~ X C _ _ _ ~C ~ ;-0,~ ~
.
.',~ , ..
.. . .. ~ . . ~ . . ~... .
~ I
o ~
o a) ~ ~ ~ ~1 ~
o o o ~
:~',<~
~ ~ ~ r : = ' . C ~ ~
Z~ ~ X ~
/.=.~ .o I 11 1 U
~ .a '~
~1 ~- ~ 151 '==
j ~ U
~: __ . - -' ~D
,, ., _ .
i~44166 ~0 .
~ +~ a) a O O O O
' ~ h +' P
/;~.<3~l ~ ~ ~ 8 ~ ~ 7~
~l le ~ I m ~-j '1144166 ~ ~ .
.
~ /.o .
H~, ~ ~ . . _ - .
q~ 0'~ ~
a .. ~
. _~ . .__ .__ ~44166 Example 28: 58 P of the disulfochloride of the compound of the formula: Cl /o~ /~3 i1 i i i1 Cl (obtained by a condensation reaction of chloranil with l-amino-2-methoxy-5-methylbenzene and subsequent chloro-sul~onation according to British Patent 815,840) are sus-pended in water and 22 P of 3-dimethylamino-1-propylamine are added, The reaction mixture is stirred for 15 hours at room temperature and finally is stirred for a further 3 hours at 60, The basic dye of the formula - Cl -i '' i ' i' ! .
c~ o/ ~ ~2~eC~2C~2C~2~\C~3~
which has precipitated, dissolves in dilute acetic acid to give a red solution and in this form dyes cotton in a red shade with good fastness properties.
Quaternisation is carried out by warming with dimethyl sulfate in dichlorobenzene at 50 - 60 and the cationic dye of the formula ~ ~ \ ~N~ / ~ ~~.~ r 3 ~ ~ ~
is obtained; when used to dye cotton, this dye gives a red shade with good fastness properties.
When the quaternisation is carried out with ethylene chlorohydrin instead of with dimethyl sulfate, a similar dye is obtained which has equally good coloris-tic properties.
When the abovementioned condensation product of chloranil and l-amino-2-methoxy-5-methylbenzene is replaced by equivalent parts of one of the condensation products listed in Table 2 below, an otherwise identical procedure yields cationic dioxazine dyes of the formula indicated in column 3; the shade of these dyes on cotton is indicated in the last column of the table, , . . . . . . . . . .
~144~66 _ .
,~ O O ~ ~ ~ ~1 _ ~ .
~ ~ ~ : :
j- U~ ~
~-\ ,3 U~ ~~ ,, ~
~.~
d~ a ~31 ~ ~ 5 .~ .
... ~ ~ C
O h ~ ~ ,Q h -.1, ~ ~ - s s ,~ ~ ~\~
I ~ `--~ ~ , ~ ! e _ ~
! L ~ ~
, ~144~66 ~ _ ~. . o ~ .
~ d ~
~i44166 Example 38: 12 P of the disulfochloride obtained accord-ing to Example 28 are suspended in 100 P of water at 0 -5 and 8 P of 2-chloroethylamine hydrochloride are added, After adding 50 P of 10% aqueous sodium hydroxide solution, the reaction mixture is stirred for a further 15 hours at room temperature, The di-2-chloroethyl-sulfamide thus obtained is filtered off with suction and stirred with 250 parts of a 50% aqueous solution of dimethylamine for 24 hours at room temperature, The basic dioxazine dye of the formula - Cl -.~ ,o\ ,-~ ~C83 I tl 11 i i1 , C8 ~ 0/ ~ ~02N~C32C82N (C83 ) ~) is isolated and quaternised to give a cationic dye, in the manner described in Example 28, Example ~9: Using the same procedure as in Example 28, 48 P of the dicarboxylic acid chloride of the compound of the formu~a Cl ~OOC~ o~
i1 i ~ i1 i Cl (obtained in accordance with U.S. Patent Specification 2,564,381) are converted to a cationic dioxazine dye of the formula Cl 3~ 3N c~2C82C~2N30C~ t 0/ ~ N/ \-~ CONE~C~2C82 2 3 Cl 2 ~S04C 3) ~4~66 this dye dyes cotton and paper in red shades with good fastness properties, Using the dioxazine-dicarboxylic acids listed in Table 3 as the starting materials, an otherwise identical procedure yields similar cationic dyes which have a 2 2CH2 ~ (CH3)3~ (SO4C~3~) in the position o~ the COOH group or groups; the shades of these dyes on cotton are given in the last column o~
the table.
_ 31 _ a) ~ a~
~ g ~ h h U~
~ _ X
~ ~ ~ 8 ;>' ~1 :~ ~ ~ -~ ~
~1441S6 ~ .. .
o ~, h . .
. ~ ~ ~ :
~:
~0 ..
~144~6G
Example 47: 50 P of chemically bleached beech sulfite are mixed with 50 P of bleached sulfite RKN 15 (freeness 22SR) and 3 P of the dye of the formula C1 c~3 o\ ,.~ /o--~ ~-0/ ~./ \o/ ~ 2NHCOC~12~ ) 2 in water (pH 6, water hardness 10 German hardness, tempera-ture 20, liquor ratio 1:40).
After stirring for 15 minutes, sheets of paper are produced on a Frank sheet-former.
The paper is dyed in a very intense red shade which is fast to light and wet processing. The waste water is completely colourless (the degree of exhaustion reaches more than 99%).
Example 48: 100 P of chemically bleached Sulfate Stora 32 (freeness 25SR) and 1 P of the dye of the formula .~ /o\ ,-~ /OC3H7 I i1 i i i1 t H7C30 o ~ ~ ~ 2 2 ~ ~ ~
are mixed in water (pH 6, water hardness 8 German hard-ness, temperature 20, liquor ratlo 1:40). After stirring ior 15 minutes, sheets of paper are produced on a Frank sheet-former. The paper has an intense ruby shade. The fast-ness to light and the wet fastness properties of dyeings are good. The waste water is virtually colourless (degree of exhaustion about 97%).
Example 49: A paper web is produced from 50% beech sulfite and 50% Sulfite RKN 15 (bleached) on a laboratory paper-making machine which operates continuously. A solution of the dye according to Example 47 is metered ~' ~ .
~441~6 continuously into the low-density pulp ten seconds before the flow box, (0,5% dyeing, liquor ratio 1:400, water hardness 10 German hardness, pH 6, temperature 20, freeness of the paper 22 SR), A level dyeing in a red shade which is of average intensity and fast to wet processing and light results, Despite the short contact time, the waste water is com-pletely colourless, Example 50: 2 P of the dye according to Example 47 are introduced into 100 P o~ chemically bleached sulfite (freeness 22 SR), After stirring for 10 minutes (at 20, pH 6, liquor ratio 1:40, water hardness 10 German hardness), 2 P of resin size are added, After stirring for a further 10 minutes, 3 P of aluminium sulfate are added, This paper pulp is stirred for a further 5 minutes and used to produce sheets on a Frank sheet-former, The paper is dyed intense red and is fast to wet processing and light, The waste water is completely colourless, Example 51: 10 P of cotton ~abric (bleached mercerised cotton) are dyed in a laboratory beam dyeing apparatus in 200 P of a liquor (water hardness 10 German hardness, pH 6, dye liquor circulated 3 times per minute) which con-tains 0.025 P of the dye according to Example 47, The temperature is first kept at 20 ~or 15 minutes and is then raised to 100 in the course of 40 minutes, A red shade of medium intensity results, The dyeing is distinguished by very good wet fastness proper-ties, The degree of exhaustion reaches about 98%,
l14 l15 1 ~
-S02-N-alXylene tCl-C4)- N - R161 A t3 in which "alkylene" is an alkylene bridge which can be interrupted by -O-, -S-, -NH- or -N- ; R14 is ; alkyl(Cl-C4) hydrogen or a substituted or unsubstituted alkyl radical;
R15 and R17 are each a substituted or unsubstituted alkyl radical (Cl-C4) or a cycloalkyl radical and R16 is a substituted or unsubstituted alkyl radical (Cl-C4), a cycloalkyl radical, an alkoxy radical or a NH2 group;
or two of the radicals R15, R16 and/or R17, together with the nitrogen atom, form a heterocyclic ring; or Z is a cationic group of the formula ,., g -CO-~ - al~ylene(Cl-C4) - ~ - R16]
R17 A~
or llS ~ A
R
_ 17 in which the symbols R14, alkylene, R15, R16 and R17 a as defined above, and in which A ~ is an anion in every case If Z is a quaternised basic group, anions A are either inorganic or organic anions; examples are:
halide ions, such as chloride, bromide or iodide ions, and sulfate, methylsulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, molybdophosphate, tungstophosphate, tungstomolybdophosphate, benzene-sulfonate, naphthalenesulfonate, 4-chlorobenzene-sulfonate, oxalate, maleate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as that of zinc chloride double salts.
Preferred anions are, depending on the way in which the compounds are used, for example the acetate ion and chloride ion (for textile and paper materials) and the chloride ion for the preparation of inks In preferred dioxazine compounds, Z is a quater-nised basic group or a radical containing such a group and n is the number 2 or 3.
An anionic group Y is, for example, the phosphoric acid group, the carboxylic acid group or the sulfonic acid group or a salt form, such as the Na, K, Li or NH4 salt, of this free acid group In preferred dioxazine compounds, m is the number O and Y is the SO3H group or a salt form thereof.
Dioxazine compounds of particular interest have the formula I in which Z is a cationic group, n is the number 2 or ~, m is the number O and X and Xl are each Cl, and in which A and Al have the same substituents.
The basic dioxazine compounds of the formula I, which can be quaternised, are compounds which are charac-terised by brilliant red to blue shades, by the fact that they are not sensitive to the degree of hardness of water and by a high affinity for, in particular, cellulose materials; furthermore, the addition of fixing agents to the application bath is not necessary for the application of these dioxazine compounds.
The basic dioxazine compounds of the formula I, which can be quaternised, are prepared in a known manner One possibility comprises, for example, a) introducing a basic group Z, which can be quate~nised, into a compound of the formula II
X
~-~ /N~ /o~
in which the symbols A, Al, X and Xl are as defined under formula I, then, if Y is not yet-present, introducing an anionic group Y if necessary and, if necessary, quaternis-ing the quaternisable basic group Z with a quaternising agent, or b~ subjecting a compound of the formula III
X' C~ o (III) O~ C1 X;
in which X~ and Xl are the same as X and Xl but are not 114~166 CN, to a condensation reaction with at least a mols of a compound A-NH2 and b mols of a compound Al-NH2, the sum of a and b being at least 2 and the said compounds A-NH2 and Al-NH2 containing n basic groups Z, which can be quaternisable, or n already quaternised basic groups Z, the reaction proceeding with cyclisation to form a dioxazine compound, quaternising a quaternisable basic group Z, which may be present, with a quaternising agent and, if necessary, introducing an anionic group Y, With regard to process variant a), the starting compounds of the formula II are known both with and with-out an anionic group Y (for example U.S. Patent Specifica-tions 2,016,504, 2,082,344 and 2,026,092) and can be obtained in a known manner. The introduction of a quaternisable basic group Z or the introduction of a group Z which contains a quaternisable group is likewise effec-ted in a known manner, for example by reacting the com-pound of the formula II with N-methylolchloroacetamide in concentrated X2S04 or phosphoric acid, if necessary in the pre~ence of P205, at 0-50C and preferably at room tem-perature, or by first introducing the S02Cl group into the compound of the formula II in a conventional manner (for example using chlorosulfonic acid at 100-150C) and then aminating, or by introducing the -CH2Cl group into the compound of the formula II and then aminating Basic groups suitable as a quaternisable basic group Z are all basic groups which are capable of taking up protons during the dyeing process so that they are con-verted to cationic groups. Examples of such compounds which introduce a basic quaternisable group Z are N-methylolchl~acetamide with subsequent reaction with an amine such as pyridine; alternatively the radical -S02Cl is first introduced into the molecule, for example using chlorosulfonic acid, and the compound is then reacted with a diamine, for example 3-dimethylamino-1-propylamine.
If it is desired to convert the quaternisable basic group ~ in the compound of the formula II into a 1149~166 quaternised group, the quaternisation is likewise e~fected in a known manner, for example using quaternising agents in an inert solvent, such as chlorobenzene, or, if desired, in aqueous suspension, or without a solvent in an excess of the quaternising agent, at a temperature of about 20 to 120C.
Suitable quaternising agents are, for example, alkyl halides, such as methyl chloride or ethyl chloride, methyl bromide, ethyl bromide or butyl bromide or methyl iodide or ethyl iodide, and in particular alkyl sulfates, such as dimethyl sulfate, diethyl sulfate and dibutyl sulfate, or benzyl chloride, chloracetamide, acrylates, epoxides, such as ethylene oxide, epichlorohydrin, alkyl esters of aromatic sulfonic acids, such as methyl p-toluenesulfonate or methyl benzenesulfonate, and also the propyl and butyl esters of benzenesulfonic acid If the compounds of the formula II do not contain an anionic group Y,these groups Y can advantageously be introduced prior to the quaternisation reaction for the conversion of the quaternisable group to a quaternised group Z. This is effected, for example, by sulfonation with sulfuric acid or, in order to introduce a phosphoric acid group, by the procedure of U.S. Patent Specification 2,845,420 After the quaternisation and the introduction of the anionic group Y, which may be carried out, the dioxazine compounds of the formula I are separated from the reaction medium and dried.
With regard to procedure b), the starting material used in this case is the compound of the formula III, which is sub~ected to a condensation reaction with a mols of A-NH2 and b mols of Al-NH2, with cyclisation, in a known manner (K,Venkataraman, Volume II (1952) page 786 "The Chemistry of Synthetic Dyes" NY ). If X and/or X
in the end product of the formula I are CN, such compounds are prepared, for example, by subjecting the compound of the formula IIIa ,., li49~66 O~ \ ~ \Cl (IIIa) to a condensation reaction with a mols of A-NH2 and b mols of Al-NH2, with cyclisation, in accordance with the above instructions, and then replacing the two Cl atoms by CN
groups, for example by reacting the condensation product with CuCN in a known manner, for example in accordance with the procedure of German Offenlegungsschrift 2,733,539 If the amines A-NH2 and Al-MH2 contain a quater-nisable basic group Z, the latter can be converted to a quaternised group by a procedure analogous to those des-cribed above; if necessary, an anionic group Y is then also introduced, as described further above Because of these process measures it is possible to prepare dioxazine compounds of the formula I in which the two symbols A have identical or different substitu-ents. In addition, it is also possible to prepare mix- -tures which contain dioxazine compounds of the formula I
in which the two symbols A have the same substituents and dioxazine compoundS of the formula I in which the two symbols A have different substituents.
The novel, basic dioxazine compounds of the for-mula I, which can be quaternised, are used as dyes for dyeing and printing textile materials, paper and leather and for preparing inks, If these dyes are used for dyeir~g and printing textile materials, the materials which can be dyed are wool, silk and acid-modified polyamide materials, and also polyacrylonitrile materials, in particular wet cable, and modified polyester material which can be dyed with basic dyes. However, the materials are in particular natural and regenerated cellulose materials, especially cotton and viscose, on which red to blue dyeings, which are brilliant in some cases, are obtained, Tne dioxazine 1144~66 compounds of the formula I according to the invention have a good uptake, good exhaustion and good build-up on these textile materials, and in particular on the said cellu-lose materials, and the resulting dyeings have very good fastness properties, in particular wet fastness properties, such as fastness to washing, and fastness to light.
With the basic dioxazine dyes, the wet fastness properties can be even further improved if necessary, by rendering the dyes insoluble, for example by means of an alkaline after-treatment on the fibre. Furthermore, it is an advantage that the dioxazine compounds of the formula I
according to the invention are taken up by the cellulose materials without pre-treatment of the said materials and without additional addition of salt to the dye liquor, The dioxazine compounds of the formula I according to the invention are also used for dyeing paper of all types, in particular bleached, unsized and sized, lignin-free paper These compounds are very particularly suit-able for dyeing unsized paper (tissues) because of their very high standard affinity for this substrate.
The dioxazine compounds according to the invention are taken up very well by these substrates and the waste water remains colourless - even in the case o~ deep shades (to more than 1/1 SD = standard depth of dyeing) -and this is an eminent technical and ecological advantage, especially with regard to the current laws relating to effluents. The good uptake is also advantageous for good reproducibility of the shade, The hardness of the water has virtually no influence on the uptake. The dyeings are fast to wet processing, i,e. they show no tendency to staining when dyed paper in the wet state is brought into contact with moist white paper. This characteristic is particularly desirable for so-called tissues, with which it is foreseeable that the dyed paper will come into contact in the wet state (for example saturated with water, alcohol, surfactant solution or the like) with other sur~aces such as textiles, paper and the ,, ~144166 like, which have to be protected against soiling The high affinity for paper and the high rate of exhaustion of the dioxazine dyes according to the inven-tion are a great advantage for the continuous dyeing of paper and thus make possible a wider application of this known, highly economical process, which has the following advantages:
a) simpler and more rapid correction of the shade and thus less loss of paper which does not conform to type (wast-age) compared with the discontinuous dyeing of paper pulp;
b) better constancy of the shade; (no "tailing") and c) if the dye is metered in just upstream of the flow box, in the low-density pulp, thorough cleaning of the beater, the blending chest and the like after each batch can be dispensed with, thus shortening the process and stream-lining the procedure at the same time.
The dioxazine compounds of the formula I are also used for dyeing leather materials by very diverse applica-tlon processes? such as spraying, brushing and immersion, and for the preparation of inks of all types, such as for ballpoint pens and printing inks Finally, the novel dioxazine compounds of the formula I are also suitable for bulk dyeing linear syn-thetic high-molecular weight polyamides, such as poly-hexamethyleneadipamide, Dyeing of the polyamide chips is effected, in particular, from an aqueous bath in the presence of wetting agents or dispersing agents and, if desired, salts, with subsequent melting and shaping.
With regard to the reducible characteristics o~
the molten high-molecular weight polyamide melts and the high melt temperature (about 270-300C), the use of these dyes of the formula I constitutes a surprising enrichment of the art.
The following examples illustrate the invention without restricting it thereto, The temperatures are in degrees centigrade and parts (P) and percentages are by weight.
~1~4166 -- 16 _ Example 1: A mixture of 57 P of the compound of the formula Cl ._.
/o~ /o-.~ ~-.~.. ;o~ C~3 Cl (the condensation product of chloranil and l-amino-2,4-o-methylphenoxy-benzene) and 28 P of N-methylolchloro-acetamide is introduced at 0-5 into 500 P of 90% sulfuric acid and the mixture is stirred at 0-5 for 15 hours.
The reaction product is precipitated on ice and is filtered off again, with suction, and washed with water After drying, this yields 72 P of the compound of the formula:
Cl I t~-`t~N~t~!~-/`-' ~t' '~ --~ca2~CC~2cl)2 ~ - 3 --~C~Cl 60 P of the product thus obtained are introduced into 400 P of pyridine and the mixture is warmed at 100 for 1 hour. The dye of the formula:
o\ ~ o_.~ ~ ~. ~ 2N~C~C~2~ ~ ~3 2 1 11 i i i1 ~ - ~/-~t~ - C~3 2Cl~
L ~ C~3 Cl which has precipitated is filtered off with suction and dried. It displays a very good uptake on paper and cotton, and the pale red dyeings have a good spectrum of fastness properties, .
.
~ . ~
li44:16~i When the above example is repeated replacing pyridine by a- or Y-picoline or by a mixture of a-/Y-picoline or by triethylenediamine or N,N-dimethylhydrazine or N,N-dimethylethanolamine, similar dyes are obtained which have equally good coloristic properties When the 57 P of the condensation product of chloranil and l-amino-2,4-o-methylphenoxy-benzene are replaced by equivalent parts of the condensation products listed in Table 1 below and these products are reacted with 28 P of N-methylolchloroacetamide and the reaction products are aminated with pyridine, an otherwise iden-tical procedure yields cationic dioxazine dyes of the formula indicated in column 3; the colour shade of these dyes on cotton is indicated in the last column of the table.
~44~66 ~ o o a) a~
o ~ h S-~ 3 :
:~: s s s ~ , . C,=.~ ~
' .
. .
I ~f ~_ _ il44166 og o c~ h ~ h _. _, U~ ~
_ --/ O ~ ~ : :' 5 ¢.~
.4 U~ O
I __ ~
. ~ . -- _ I ~5 ~ ~--~ a ~ a .~ __ _ . ..
1~ ~D r t~ ~ O
.. .
~144166 O g ~1 ~0 ~ ~ ~ ~ O
o h ~ h h 5 ~ o ~ s ~ , .
¦ ~ ~ ~ C' ~
~ ~._.~" . _ _ I ~ 0 r X -- ~ ~ ~ X C _ _ _ ~C ~ ;-0,~ ~
.
.',~ , ..
.. . .. ~ . . ~ . . ~... .
~ I
o ~
o a) ~ ~ ~ ~1 ~
o o o ~
:~',<~
~ ~ ~ r : = ' . C ~ ~
Z~ ~ X ~
/.=.~ .o I 11 1 U
~ .a '~
~1 ~- ~ 151 '==
j ~ U
~: __ . - -' ~D
,, ., _ .
i~44166 ~0 .
~ +~ a) a O O O O
' ~ h +' P
/;~.<3~l ~ ~ ~ 8 ~ ~ 7~
~l le ~ I m ~-j '1144166 ~ ~ .
.
~ /.o .
H~, ~ ~ . . _ - .
q~ 0'~ ~
a .. ~
. _~ . .__ .__ ~44166 Example 28: 58 P of the disulfochloride of the compound of the formula: Cl /o~ /~3 i1 i i i1 Cl (obtained by a condensation reaction of chloranil with l-amino-2-methoxy-5-methylbenzene and subsequent chloro-sul~onation according to British Patent 815,840) are sus-pended in water and 22 P of 3-dimethylamino-1-propylamine are added, The reaction mixture is stirred for 15 hours at room temperature and finally is stirred for a further 3 hours at 60, The basic dye of the formula - Cl -i '' i ' i' ! .
c~ o/ ~ ~2~eC~2C~2C~2~\C~3~
which has precipitated, dissolves in dilute acetic acid to give a red solution and in this form dyes cotton in a red shade with good fastness properties.
Quaternisation is carried out by warming with dimethyl sulfate in dichlorobenzene at 50 - 60 and the cationic dye of the formula ~ ~ \ ~N~ / ~ ~~.~ r 3 ~ ~ ~
is obtained; when used to dye cotton, this dye gives a red shade with good fastness properties.
When the quaternisation is carried out with ethylene chlorohydrin instead of with dimethyl sulfate, a similar dye is obtained which has equally good coloris-tic properties.
When the abovementioned condensation product of chloranil and l-amino-2-methoxy-5-methylbenzene is replaced by equivalent parts of one of the condensation products listed in Table 2 below, an otherwise identical procedure yields cationic dioxazine dyes of the formula indicated in column 3; the shade of these dyes on cotton is indicated in the last column of the table, , . . . . . . . . . .
~144~66 _ .
,~ O O ~ ~ ~ ~1 _ ~ .
~ ~ ~ : :
j- U~ ~
~-\ ,3 U~ ~~ ,, ~
~.~
d~ a ~31 ~ ~ 5 .~ .
... ~ ~ C
O h ~ ~ ,Q h -.1, ~ ~ - s s ,~ ~ ~\~
I ~ `--~ ~ , ~ ! e _ ~
! L ~ ~
, ~144~66 ~ _ ~. . o ~ .
~ d ~
~i44166 Example 38: 12 P of the disulfochloride obtained accord-ing to Example 28 are suspended in 100 P of water at 0 -5 and 8 P of 2-chloroethylamine hydrochloride are added, After adding 50 P of 10% aqueous sodium hydroxide solution, the reaction mixture is stirred for a further 15 hours at room temperature, The di-2-chloroethyl-sulfamide thus obtained is filtered off with suction and stirred with 250 parts of a 50% aqueous solution of dimethylamine for 24 hours at room temperature, The basic dioxazine dye of the formula - Cl -.~ ,o\ ,-~ ~C83 I tl 11 i i1 , C8 ~ 0/ ~ ~02N~C32C82N (C83 ) ~) is isolated and quaternised to give a cationic dye, in the manner described in Example 28, Example ~9: Using the same procedure as in Example 28, 48 P of the dicarboxylic acid chloride of the compound of the formu~a Cl ~OOC~ o~
i1 i ~ i1 i Cl (obtained in accordance with U.S. Patent Specification 2,564,381) are converted to a cationic dioxazine dye of the formula Cl 3~ 3N c~2C82C~2N30C~ t 0/ ~ N/ \-~ CONE~C~2C82 2 3 Cl 2 ~S04C 3) ~4~66 this dye dyes cotton and paper in red shades with good fastness properties, Using the dioxazine-dicarboxylic acids listed in Table 3 as the starting materials, an otherwise identical procedure yields similar cationic dyes which have a 2 2CH2 ~ (CH3)3~ (SO4C~3~) in the position o~ the COOH group or groups; the shades of these dyes on cotton are given in the last column o~
the table.
_ 31 _ a) ~ a~
~ g ~ h h U~
~ _ X
~ ~ ~ 8 ;>' ~1 :~ ~ ~ -~ ~
~1441S6 ~ .. .
o ~, h . .
. ~ ~ ~ :
~:
~0 ..
~144~6G
Example 47: 50 P of chemically bleached beech sulfite are mixed with 50 P of bleached sulfite RKN 15 (freeness 22SR) and 3 P of the dye of the formula C1 c~3 o\ ,.~ /o--~ ~-0/ ~./ \o/ ~ 2NHCOC~12~ ) 2 in water (pH 6, water hardness 10 German hardness, tempera-ture 20, liquor ratio 1:40).
After stirring for 15 minutes, sheets of paper are produced on a Frank sheet-former.
The paper is dyed in a very intense red shade which is fast to light and wet processing. The waste water is completely colourless (the degree of exhaustion reaches more than 99%).
Example 48: 100 P of chemically bleached Sulfate Stora 32 (freeness 25SR) and 1 P of the dye of the formula .~ /o\ ,-~ /OC3H7 I i1 i i i1 t H7C30 o ~ ~ ~ 2 2 ~ ~ ~
are mixed in water (pH 6, water hardness 8 German hard-ness, temperature 20, liquor ratlo 1:40). After stirring ior 15 minutes, sheets of paper are produced on a Frank sheet-former. The paper has an intense ruby shade. The fast-ness to light and the wet fastness properties of dyeings are good. The waste water is virtually colourless (degree of exhaustion about 97%).
Example 49: A paper web is produced from 50% beech sulfite and 50% Sulfite RKN 15 (bleached) on a laboratory paper-making machine which operates continuously. A solution of the dye according to Example 47 is metered ~' ~ .
~441~6 continuously into the low-density pulp ten seconds before the flow box, (0,5% dyeing, liquor ratio 1:400, water hardness 10 German hardness, pH 6, temperature 20, freeness of the paper 22 SR), A level dyeing in a red shade which is of average intensity and fast to wet processing and light results, Despite the short contact time, the waste water is com-pletely colourless, Example 50: 2 P of the dye according to Example 47 are introduced into 100 P o~ chemically bleached sulfite (freeness 22 SR), After stirring for 10 minutes (at 20, pH 6, liquor ratio 1:40, water hardness 10 German hardness), 2 P of resin size are added, After stirring for a further 10 minutes, 3 P of aluminium sulfate are added, This paper pulp is stirred for a further 5 minutes and used to produce sheets on a Frank sheet-former, The paper is dyed intense red and is fast to wet processing and light, The waste water is completely colourless, Example 51: 10 P of cotton ~abric (bleached mercerised cotton) are dyed in a laboratory beam dyeing apparatus in 200 P of a liquor (water hardness 10 German hardness, pH 6, dye liquor circulated 3 times per minute) which con-tains 0.025 P of the dye according to Example 47, The temperature is first kept at 20 ~or 15 minutes and is then raised to 100 in the course of 40 minutes, A red shade of medium intensity results, The dyeing is distinguished by very good wet fastness proper-ties, The degree of exhaustion reaches about 98%,
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A dioxazine compound of the formula I
(I) in which X and X1 independently of each other are identical or different substituents from the category comprising: 1) hydrogen, 2) halogen, 3) cyano, 4) unsubstituted alkyl C1-C4, 5) unsubsti-tuted phenyl, 6) phenyl substituted by halogen or alkyl C1-C4, 7)-NHCOR1, wherein R1 is alkyl C1-C4, cycloalkyl, unsubstituted aryl, aryl which is substituted by alkyl C1-C4, or halogen, or R1 is a heterocyclic radical selected from furan, thiophen, pyridine, quinoline, phenylthiazole or phenyltriazole, 8) OCOR2 in which R2 is unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by phenyl or R2 is cycloalkyl, 9) -CONR4.R5 wherein R4 and R5 independently of one another are hydrogen, unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by phenyl or-NT1T2 OR-NR15.R16.R17 or R4 and/or R5 is cycloalkyl or aryl or R4 together with R5 and with the inclusion of the N-atom forms a pyrrolidine, piperidine or morpholine ring, 10) -COOR6 wherein R6 is hydrogen, unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by OH and phenyl or R6 is cycloalkyl; Y represents an anionic group selected from the phosphoric acid group, the carboxylic acid group or the sulfonic acid group or a salt form of such a free acid group; benzene nuclei A and Al are optionally substituted by: A) halogen, B) cyano, C) NO2, D) SCN, E) unsub-stituted alkyl C1-C8, F) alkyl C1-C8 substituted by phenyl, G) unsubstituted phenyl, H) phenyl substituted by halogen, COOH, NO2, NH2, NHalkyl C1-C4, N(alkyl C1-C4)2,alkyl C1-C4, alkoxy C1-C4, NHCOphenyl or NHCOalkyl C1-C4, I) NHCOR18 wherein R18 is unsubstituted alkyl C1-C4, alkyl C1-C4 which is substituted by alkoxy C1-C4, cycloalkyl, OH or phenyl which phenyl is either unsubstituted or substituted by halogen, alkoxy C1-C4, alkyl C1-C4, NO2 or CN, or R18 is alkoxy C1-C4 or cycloalkyl or unsub-stituted aryl or aryl which is substituted by chloro or OCH3, K) unsubstituted benzthiazole or benzthiazole which is substituted by unsubstituted alkyl C1-C4, unsubstituted alkoxy C1-C4 or alkoxy C1-C4 which is substituted by alkoxy C1-C4, OH or phenyl, L) unsubstituted alkoxy C1-C4 or alkoxy C1-C4 which is substituted by OH, alkyl C1-C4 or alkoxy C1-C4, M) unsubstituted phenoxy or phenoxy which is substituted by alkyl C1-C4, N) NHR19 wherein R19 is hydrogen, unsubstituted aryl or aryl which is condensed with a benzoxazole, benzthiazole or benzimidazole nucleus, or R19 is benzthiazole, O) SO2alkyl C1-C4, P) CONHR20 wherein R20 is unsubstituted aryl or aryl which is substituted by halogen, phenyl or alkyl C1-C4; Z is either a basic group of the formula or or or a quaternised group according to the formula -CH2-NH-CO-alkylene(C1-C4)-K? A?
or a quaternised group according to the formula or or in which formulae the symbols have the following meaning: T1 is H or alkyl C1-C4, which is unsubstituted or substituted by hydroxyl, or T1 is cyclohexyl, unsubstituted or substituted by 1 to 3 methyl radicals, or T1 is phenyl and T2 is alkyl C1-C4, which is unsubstituted or substituted by hydroxyl, or the radicals T1 and T2 together with the N atom can also form a pyrrolidine, pyridine, morpholine or piperazine ring, and W is hydrogen, unsubstituted alkyl C1-C4 or alkyl C1-C4 substituted by OH or alkoxy C1-C4, * ? is a radical of the formula or wherein R7 and R8 independently of one another are unsubstituted alkyl C1-C4, alkyl C1-C4 substituted by OH, CONH2 or CN or unsubstituted cycloalkyl, R9 and R10 independently of each other are hydrogen, unsubstituted alkyl C1-C4, cycloalkyl or acyl, R11 is hydrogen, unsubstituted alkyl C1-C4, alkyl C1-C4 substituted by OH, unsubstituted cycloalkyl or unsubstituted aryl, and R12 is hydrogen, unsubstituted alkyl C1-C4, alkyl C1-C4 substituted by OH, unsubstituted cycloalkyl, unsubstituted alkoxy C1-C4 or unsubstituted aryl, R13 is unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by OH, CONH2, NH2 or R13 is alkoxy C1-C4, or R7 and R8 or R7 and R9 or R8 and R10 or R11 and R12 together with the N atom, form a piperidine, pyrrolidine or morpholine ring or R11, R12 and R13 with the inclusion of the N atom form a heterocyclic ring of the formula:
unsubstituted pyridine or pyridine which is substituted by CH3, OH, NH2, COOH or CN, R14 is hydrogen or unsubstituted alkyl C1-C4, R15 and R17 are each unsubstituted alkyl C1-C4 or cycloalkyl and R16 is unsubstituted alkyl C1-C4, cycloalkyl, alkoxy C1-C4 or NH2, or two of the radicals R15, R16 and/or R17, together with the nitrogen atom, form an unsubstituted pyridine ring or pyridine which is substituted by CH3, OH, NH2, COOH or CN; n is a number from 1 to 4 and m is a number from O to 2, with the proviso that the number m is smaller than n.
(I) in which X and X1 independently of each other are identical or different substituents from the category comprising: 1) hydrogen, 2) halogen, 3) cyano, 4) unsubstituted alkyl C1-C4, 5) unsubsti-tuted phenyl, 6) phenyl substituted by halogen or alkyl C1-C4, 7)-NHCOR1, wherein R1 is alkyl C1-C4, cycloalkyl, unsubstituted aryl, aryl which is substituted by alkyl C1-C4, or halogen, or R1 is a heterocyclic radical selected from furan, thiophen, pyridine, quinoline, phenylthiazole or phenyltriazole, 8) OCOR2 in which R2 is unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by phenyl or R2 is cycloalkyl, 9) -CONR4.R5 wherein R4 and R5 independently of one another are hydrogen, unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by phenyl or-NT1T2 OR-NR15.R16.R17 or R4 and/or R5 is cycloalkyl or aryl or R4 together with R5 and with the inclusion of the N-atom forms a pyrrolidine, piperidine or morpholine ring, 10) -COOR6 wherein R6 is hydrogen, unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by OH and phenyl or R6 is cycloalkyl; Y represents an anionic group selected from the phosphoric acid group, the carboxylic acid group or the sulfonic acid group or a salt form of such a free acid group; benzene nuclei A and Al are optionally substituted by: A) halogen, B) cyano, C) NO2, D) SCN, E) unsub-stituted alkyl C1-C8, F) alkyl C1-C8 substituted by phenyl, G) unsubstituted phenyl, H) phenyl substituted by halogen, COOH, NO2, NH2, NHalkyl C1-C4, N(alkyl C1-C4)2,alkyl C1-C4, alkoxy C1-C4, NHCOphenyl or NHCOalkyl C1-C4, I) NHCOR18 wherein R18 is unsubstituted alkyl C1-C4, alkyl C1-C4 which is substituted by alkoxy C1-C4, cycloalkyl, OH or phenyl which phenyl is either unsubstituted or substituted by halogen, alkoxy C1-C4, alkyl C1-C4, NO2 or CN, or R18 is alkoxy C1-C4 or cycloalkyl or unsub-stituted aryl or aryl which is substituted by chloro or OCH3, K) unsubstituted benzthiazole or benzthiazole which is substituted by unsubstituted alkyl C1-C4, unsubstituted alkoxy C1-C4 or alkoxy C1-C4 which is substituted by alkoxy C1-C4, OH or phenyl, L) unsubstituted alkoxy C1-C4 or alkoxy C1-C4 which is substituted by OH, alkyl C1-C4 or alkoxy C1-C4, M) unsubstituted phenoxy or phenoxy which is substituted by alkyl C1-C4, N) NHR19 wherein R19 is hydrogen, unsubstituted aryl or aryl which is condensed with a benzoxazole, benzthiazole or benzimidazole nucleus, or R19 is benzthiazole, O) SO2alkyl C1-C4, P) CONHR20 wherein R20 is unsubstituted aryl or aryl which is substituted by halogen, phenyl or alkyl C1-C4; Z is either a basic group of the formula or or or a quaternised group according to the formula -CH2-NH-CO-alkylene(C1-C4)-K? A?
or a quaternised group according to the formula or or in which formulae the symbols have the following meaning: T1 is H or alkyl C1-C4, which is unsubstituted or substituted by hydroxyl, or T1 is cyclohexyl, unsubstituted or substituted by 1 to 3 methyl radicals, or T1 is phenyl and T2 is alkyl C1-C4, which is unsubstituted or substituted by hydroxyl, or the radicals T1 and T2 together with the N atom can also form a pyrrolidine, pyridine, morpholine or piperazine ring, and W is hydrogen, unsubstituted alkyl C1-C4 or alkyl C1-C4 substituted by OH or alkoxy C1-C4, * ? is a radical of the formula or wherein R7 and R8 independently of one another are unsubstituted alkyl C1-C4, alkyl C1-C4 substituted by OH, CONH2 or CN or unsubstituted cycloalkyl, R9 and R10 independently of each other are hydrogen, unsubstituted alkyl C1-C4, cycloalkyl or acyl, R11 is hydrogen, unsubstituted alkyl C1-C4, alkyl C1-C4 substituted by OH, unsubstituted cycloalkyl or unsubstituted aryl, and R12 is hydrogen, unsubstituted alkyl C1-C4, alkyl C1-C4 substituted by OH, unsubstituted cycloalkyl, unsubstituted alkoxy C1-C4 or unsubstituted aryl, R13 is unsubstituted alkyl C1-C4 or alkyl C1-C4 which is substituted by OH, CONH2, NH2 or R13 is alkoxy C1-C4, or R7 and R8 or R7 and R9 or R8 and R10 or R11 and R12 together with the N atom, form a piperidine, pyrrolidine or morpholine ring or R11, R12 and R13 with the inclusion of the N atom form a heterocyclic ring of the formula:
unsubstituted pyridine or pyridine which is substituted by CH3, OH, NH2, COOH or CN, R14 is hydrogen or unsubstituted alkyl C1-C4, R15 and R17 are each unsubstituted alkyl C1-C4 or cycloalkyl and R16 is unsubstituted alkyl C1-C4, cycloalkyl, alkoxy C1-C4 or NH2, or two of the radicals R15, R16 and/or R17, together with the nitrogen atom, form an unsubstituted pyridine ring or pyridine which is substituted by CH3, OH, NH2, COOH or CN; n is a number from 1 to 4 and m is a number from O to 2, with the proviso that the number m is smaller than n.
2. A dioxazine compound of the formula I according to claim 1, wherein Z is a quaternised basic group.
3. A dioxazine compound according to claim 2, wherein Z
is one of the following cationic groups:
-CH2-NH-CO-alkylene(C1-C4)-K? A?
in which K? is a radical of the formula or in which R7 to R13 are as defined in claim 1; or Z is a cationic group of the formula in which "alkylene" is an alkylene bridge which can be interrupted by -O-, -S-, -NH- or -N- and R14 to R17 are as defined alkyl(C1-C4) in claim 1;
or Z is a cationic group of the formula or in which the symbols R14, alkylene, R15, R16 and R17 are as defined above, and in which A- is an anion in every case.
is one of the following cationic groups:
-CH2-NH-CO-alkylene(C1-C4)-K? A?
in which K? is a radical of the formula or in which R7 to R13 are as defined in claim 1; or Z is a cationic group of the formula in which "alkylene" is an alkylene bridge which can be interrupted by -O-, -S-, -NH- or -N- and R14 to R17 are as defined alkyl(C1-C4) in claim 1;
or Z is a cationic group of the formula or in which the symbols R14, alkylene, R15, R16 and R17 are as defined above, and in which A- is an anion in every case.
4. A dioxazine compound of the formula I according to claim 1, wherein n is the number 2 or 3.
5, A dioxazine compound of the formula I according to claim 1, wherein m is the number 0.
6. A dioxazine compound of the formula I according to claim 1, wherein X and X1 are identical substituents.
7. A dioxazine compound of the formula I according to claim 6, wherein X and X1 are each the group NHCORl, in which R1 is alkyl (C1-C4), unsubstituted aryl or aryl substituted by alkyl (C1-C4) or halogen, or wherein X and X1 are each halogen.
8. A dioxazine compound of the formula I according to claim 7, wherein X and X1 are each chlorine.
9. A dioxazine compound of the formula I according to claim 1, wherein the two benzo radicals A and A1 are substituted by one or more identical substituents.
10. A dioxazine compound of the formula I according to claim 1, wherein A and A1 are substituted by the following substituents: halogen, CN, substituted or unsubstituted alkyl (C1-C8) substituted or unsubstituted phenyl, NHCOR18, in which R18 is substituted or unsubstituted alkyl, alkoxy, cycloalkyl or substituted or unsubstituted aryl, or NO2, SCN, a heterocyclic ring, a sub-stituted or unsubstituted alkoxy group, a substituted or unsubstituted phenoxy group, the group NHR19, in which R19 is hydrogen, aryl or a hetero-ring, or an alkylsulfonyl group, or the group CONHR20, in which R20 is substituted or unsubstituted aryl, substituents in each case being as specified in claim 1.
11. A dioxazine compound according to claim 10, wherein the benzo radicals A and Al are monosubstituted or polysubstituted by C1, NHCOC6H5, NHCOC6H4C1, NHCOC6H40CH3, alkoxy (C1-C3), alkoxy (C1-C3) substituted by OH or alkoxy or by alkyl, -OC6H5, -O-C6H4-CH3, -C6H5, -CH2-C6H5 and -NHCO-alkyl.
12. A dioxazine compound according to claim 11, wherein the benzo radicals A and A1 are mono- or polysubstituted by methyl-substituted alkoxy or by -NHCO-C3H7.
13. A dioxazine compound according to claim 1, wherein Z is a cationic group, n is the number 2 or 3, m is the number O, X and X1 are each C1 and A and A1 have identical substituents and are substituted by the substituents indicated in claim 11.
14. A process for the preparation of a dioxazine compound of the formula I
according to claim 1, which comprises a) introducing a basic group Z, which can be quaternised, into a compound of the formula II
(II) in which the symbols A, A1, X and X1 are as defined under formula I, then, if Y is not yet present, introducing an anionic group Y if necessary and, if necessary, quaternising the quaternisable basic group Z with a quaternising agent, or b) subjecting a compound of the formula III
(III) in which X' and X1 are the same as X and X1 but are not CN, to a condensation reaction with at least a mols of a compound A-NH2 and b mols of a compound A1-NH2, the sum of a and b being at least 2 and the said compounds A-NH2 and A1-NH2 containing n basic groups Z, which can be quaternisable, or n already quaternized basic groups Z, the reaction proceeding with cyclisation to form a dioxazine compound, quaternising a quaternisable basic group Z, which may be present, with a quaternising agent and, i necessary, introducing an anionic group Y, or subjecting the compound of the formula IIIa (IIIa) to a condensation reaction with a mols of A-NH2 and b mols of A1-NH2, with cyclisation, in accordance with the above instructions, and then replacing the two C1 atoms by CN groups.
according to claim 1, which comprises a) introducing a basic group Z, which can be quaternised, into a compound of the formula II
(II) in which the symbols A, A1, X and X1 are as defined under formula I, then, if Y is not yet present, introducing an anionic group Y if necessary and, if necessary, quaternising the quaternisable basic group Z with a quaternising agent, or b) subjecting a compound of the formula III
(III) in which X' and X1 are the same as X and X1 but are not CN, to a condensation reaction with at least a mols of a compound A-NH2 and b mols of a compound A1-NH2, the sum of a and b being at least 2 and the said compounds A-NH2 and A1-NH2 containing n basic groups Z, which can be quaternisable, or n already quaternized basic groups Z, the reaction proceeding with cyclisation to form a dioxazine compound, quaternising a quaternisable basic group Z, which may be present, with a quaternising agent and, i necessary, introducing an anionic group Y, or subjecting the compound of the formula IIIa (IIIa) to a condensation reaction with a mols of A-NH2 and b mols of A1-NH2, with cyclisation, in accordance with the above instructions, and then replacing the two C1 atoms by CN groups.
15. A method of dyeing and printing textile materials, paper or leather or for preparing inks or for bulk-dyeing linear synthetic high-molecular weight polyamides, which comprises employing a dioxazine compound of the formula I
according to claim 1 as a dye.
according to claim 1 as a dye.
16. A method of dyeing and printing natural and regenerated cellulose material, without the addition of salt, which comprises employing a dioxazine compound of the formula I according to claim 1 as a dye.
17. A method according to claim 16, wherein the cellulose material is cotton or viscose.
18. A method of dyeing and printing paper of any type, which comprises employing a dioxazine compound according to claim 1 as dye.
19. A method of dyeing and printing lignin-free, bleached and unsized paper (tissue), which comprises employing as a dye a dioxazine compound accord-ing to claim 1.
20. A method of dyeing and printing natural polyamide material or modified polyamide which can be dyed with basic dyes, which comprises employing as a dye a dioxazine compound according to claim 1.
21. A method according to claim 20, wherein the natural polyamide material is wool or silk.
22. A method of dyeing and printing polyacrylonitrile material, which comprises employing as a dye a dioxazine compound according to claim 1.
23. A method of dyeing and printing modified polyester material which can be dyed with basic dyes, which comprises employing as a dye a dioxazine compound according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH104179 | 1979-02-02 | ||
| CH1041/79-8 | 1979-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144166A true CA1144166A (en) | 1983-04-05 |
Family
ID=4201075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000344817A Expired CA1144166A (en) | 1979-02-02 | 1980-01-31 | Basic dioxazine compounds |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4336377A (en) |
| EP (1) | EP0015232B1 (en) |
| JP (1) | JPS55104351A (en) |
| BR (1) | BR8000641A (en) |
| CA (1) | CA1144166A (en) |
| DE (1) | DE3063216D1 (en) |
| ES (1) | ES488197A0 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3026948A1 (en) * | 1980-07-16 | 1982-02-11 | Hoechst Ag, 6000 Frankfurt | METHOD FOR DYEING FIBER GOODS FROM WET-WOVEN ACRYLNITRILE POLYMERISATES IN A GEL STATE |
| DE3026946A1 (en) * | 1980-07-16 | 1982-02-11 | Hoechst Ag, 6000 Frankfurt | METHOD FOR COLORING FIBER GOODS FROM DRY-SPUN ACRYLNITRILE POLYMERISATES IN THE GEL STATE |
| DE3026947A1 (en) * | 1980-07-16 | 1982-02-11 | Hoechst Ag, 6000 Frankfurt | METHOD FOR COLORING FIBER GOODS FROM GEL STATE OF ACRYLNITRILE POLYMERISATS SPORN FROM ORGANIC SOLVENTS |
| DE3117956A1 (en) * | 1981-05-07 | 1982-11-25 | Basf Ag, 6700 Ludwigshafen | CATIONIC DYES AND THEIR USE FOR COLORING AND PRINTING PAPER |
| EP0095255A3 (en) * | 1982-05-24 | 1984-02-29 | Imperial Chemical Industries Plc | Triphendioxazine dyes, methods for their manufacture and their use for dyeing cellulosic substrates |
| DE3336362A1 (en) * | 1983-10-06 | 1985-04-18 | Bayer Ag, 5090 Leverkusen | TRIPHENDIOXAZINE REACTIVE DYES |
| US4629788A (en) * | 1983-10-11 | 1986-12-16 | Bayer Aktiengesellschaft | Triphendioxazine reactive dyestuffs |
| DE3341886A1 (en) * | 1983-11-19 | 1985-05-30 | Bayer Ag, 5090 Leverkusen | BASIC TRIPHENDIOXAZINE DYES, THEIR PRODUCTION AND USE |
| DE3344254A1 (en) * | 1983-12-07 | 1985-06-20 | Bayer Ag, 5090 Leverkusen | TRIPHENDIOXAZINE DYES |
| DE3344472A1 (en) * | 1983-12-08 | 1985-06-20 | Bayer Ag, 5090 Leverkusen | BASIC TRIPHENDIOXAZINE DYES, THEIR PRODUCTION AND USE |
| DE3439756A1 (en) * | 1984-02-11 | 1985-08-14 | Bayer Ag, 5090 Leverkusen | TRIPHENDIOXAZINE VINYL SULPHONE DYES |
| DE3409439A1 (en) * | 1984-03-15 | 1985-09-26 | Bayer Ag, 5090 Leverkusen | TRIPHENDIOXAZINE DYES |
| DE3439755A1 (en) * | 1984-04-05 | 1985-10-17 | Bayer Ag, 5090 Leverkusen | TRIPHENDIOXAZINE DYES |
| DE3423581A1 (en) * | 1984-06-27 | 1986-01-09 | Bayer Ag, 5090 Leverkusen | REACTIVE DYES |
| DE3426727A1 (en) * | 1984-07-20 | 1986-01-23 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE TRIPHENDIOXAZINE COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| FR2572382B1 (en) * | 1984-10-25 | 1989-11-24 | Sandoz Sa | NOVEL OXAZINIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS DYES |
| DE3832531A1 (en) * | 1988-09-24 | 1990-03-29 | Bayer Ag | DIRECT COLORS |
| DE3917257A1 (en) * | 1989-05-26 | 1990-11-29 | Basf Ag | TETRACHLOROFERRATE OF BASIC DYES |
| DE102004001883A1 (en) * | 2004-01-14 | 2005-08-11 | Clariant Gmbh | triphendioxazine |
| FR3022253B1 (en) * | 2014-06-16 | 2016-07-01 | SOCIéTé BIC | PHOTORETICULABLE WRITING INK |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2863875A (en) * | 1953-12-21 | 1958-12-09 | Bayer Ag | Process for the production of basic dyestuffs |
| GB784844A (en) * | 1954-12-21 | 1957-10-16 | Bayer Ag | Dyeing process |
| GB850159A (en) * | 1958-04-16 | 1960-09-28 | Bayer Ag | Water-soluble sulphonium dyestuffs |
| FR1298841A (en) * | 1960-08-30 | 1962-07-13 | Hoechst Ag | Process for dyeing and printing shaped articles made of polyacrylonitrile |
| DE1223336B (en) | 1960-08-30 | 1966-08-25 | Hoechst Ag | Process for coloring and printing molded structures made of polyacrylonitrile |
| CH453543A (en) | 1963-12-31 | 1968-06-14 | Sandoz Ag | Process for the preparation of hydrazine derivatives |
| DE1286666B (en) * | 1962-04-05 | 1969-01-09 | Hoechst Ag | Process for the production of water-soluble, cationic dyes |
| CH485806A (en) * | 1964-08-28 | 1970-02-15 | Sandoz Ag | Process for the production of basic dyes |
| DE1619479A1 (en) * | 1966-06-10 | 1971-07-15 | Bayer Ag | Process for dyeing fully synthetic and semi-synthetic fiber materials |
| US3671529A (en) * | 1969-08-20 | 1972-06-20 | Sandoz Ltd | Basic anthraquinone dyes, with pyridinium 2- or 4-dimethylene group |
| CH565834A5 (en) * | 1972-05-09 | 1975-08-29 | Ciba Geigy Ag | |
| GB1384749A (en) * | 1972-09-06 | 1975-02-19 | Ici Ltd | Reactive dyestuffs |
| CH572548B5 (en) * | 1974-04-29 | 1976-02-13 | Ciba Geigy Ag |
-
1980
- 1980-01-28 DE DE8080810024T patent/DE3063216D1/en not_active Expired
- 1980-01-28 EP EP80810024A patent/EP0015232B1/en not_active Expired
- 1980-01-28 US US06/116,196 patent/US4336377A/en not_active Expired - Lifetime
- 1980-01-31 CA CA000344817A patent/CA1144166A/en not_active Expired
- 1980-02-01 ES ES488197A patent/ES488197A0/en active Granted
- 1980-02-01 BR BR8000641A patent/BR8000641A/en unknown
- 1980-02-02 JP JP1195780A patent/JPS55104351A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55104351A (en) | 1980-08-09 |
| ES8102586A1 (en) | 1981-02-16 |
| EP0015232A1 (en) | 1980-09-03 |
| ES488197A0 (en) | 1981-02-16 |
| US4336377A (en) | 1982-06-22 |
| DE3063216D1 (en) | 1983-07-07 |
| EP0015232B1 (en) | 1983-05-18 |
| BR8000641A (en) | 1980-10-21 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |